Palladium-catalyzed Active Unsaturated Carbon-carbon Bond Difunctionalization

Transition-metal catalyzed carbon-hetero bond and carbon-carbon bond formation is an important research direction of modern organic chemistry.In recent years,as one of the hot areas of transition-metal catalysis,palladium catalysis has attracted the attention of organic chemists.Compared with the traditional transition-metal catalysts,such as rhodium,iridium and platinum,palladium catalyst was more economic and efficient.As a basic structural unit of organic compounds,the functionalization of carbon-carbon double bond has always been the focus of organic chemistry research.Although palladium catalyzed reaction has become more and more mature in recent decades,it is worth noting that there are still many areas for further expansion and enrichment.It is still a challenging research topic to realize the efficient construction of multi-functionalized olefin double bond by palladium catalysis and to meet the needs of synthetic economy and environmental protection in the new era.In this thesis,we studied the palladium catalyzed synthesis of functionalized carbon carbon double bonds from the following three aspects.This article consists of four chapters:In the first chapter,we introducted the progress of palladium catalyzed C-H bond alkylation and arylation of olefin,palladium catalyzed arylation of allene,synthesis of pyrone structure from enynoate,coupling reactions with propanol as coupling partner,and synthesis of mult-substituted indenoisoquinoline.In the second chapter,we realized an efficient and universal methodology synthesizing tetra-substituted alkenes through a palladium-catalyzed oxyarylation reaction.Using aryl iodide as arylation reagent and palladium acetate as catalyst,we could control the acryloxy group of the product with adjunction of different acid.Thus,enough flexibility was reserved for subsequent derivatizations and potential applications as building blocks.In the third chapter,a Pd(Ⅱ)-catalyzed mild and highly regioselective 6-endo cyclization/allylation reactions of enynoates with simple allylic alcohols has been developed.Under mild reaction conditions,the vinyl palladium species generated in situ after cyclization could insert C-C double bond of allylic alcohol through cross-coupling reaction and lead to the formation of allyl pyrone via β-OH elimination.This cascade cross-coupling reaction represents a direct and atom economic methodology for the construction of novel allyl pyrones in moderate to good yields.In the fourth chapter,we developed a palladium-catalyzed intramolecular diarylation reaction of allene to achieve a one-step synthesis of substituted indenoisoquinoline.This reaction represents a new efficient and universal methodology for the synthesis of substituted indenoisoquinolines under simple condition.The yields were much higher than the traditional route,which promotes efficient synthesis and major application of indenoisoquinoline type medicine.